Fungicides

ABSTRACT

Fungicidal compounds having the formula (I): ##STR1## in which any two of K, L and M are nitrogen and the other is CA wherein A is H, halogen, C 1-4  alkyl, cyano, nitro or trifluoromethyl; X is a linking group other than oxygen; T is oxygen or sulphur; and Z is an optionally substituted carbocyclic or heterocyclic ring.

This application is a continuation of copending application Ser. No.08/118,410, filed Sep. 8, 1993, which in turn is a continuation of Ser.No. 07/779,413, filed Oct. 15, 1991, now abandoned.

This invention relates to derivatives of propenoic acid useful asfungicides, to processes for preparing them, to fungicidal compositionscontaining them, and to methods of using them to combat fungi,especially fungal infections of plants.

There is described in EP-A-0260794 a range of fungicidal compounds whichare methyl 2-(optionally substituted)heterocyclyloxy(orthio)phenyl-3-methoxypropenoates. The heterocyclic ring is six-membered,C-linked and contains 2 to 4 nitrogen atoms. Included are triazinyloxycompounds.

According to the present invention there are provided compounds havingthe formula (I), in which any two of K, L and M are nitrogen and theother is CA wherein A is H, halogen, C₁₋₄ alkyl (for example, methyl),C₁₋₄ alkoxy (for example, methoxy), cyano, nitro or trifluoromethyl; Xis a linking group other than oxygen; T is oxygen or sulphur; and Z isan optionally substituted carbocyclic or heterocyclic ring.

Because of the unsymmetrically substituted double bond of the propenoategroup, the compounds of the invention may be obtained in the form ofmixtures of (E)- and (Z)-geometric isomers. However, these mixtures canbe separated into individual isomers, and this invention embraces suchisomers and mixtures thereof in all proportions including those whichconsist substantially of the (Z)-isomer and those which consistsubstantially of the (E)-isomer. The (E)-isomer, in which the groups--CO₂ CH₃ and --OCH₃ are on opposite sides of the olefinic bond of thepropenoate group, are the more fungicidally active and form a preferredembodiment of the invention.

The ring containing K, L and M in formula (I) is a triazine ring. It maybe a symmetrical triazine ring in which K and M are both nitrogen and Lis CA or an unsymmetrical triazine ring in which either K and L are bothnitrogen and M is CA or L and M are both nitrogen and K is CA.

The group A is typically H or halogen, suitably chlorine.

The group X may be, for example, S(O)_(n), NR⁴, N(CHO), CR¹ R², CHR⁶,CO, CR¹ (OR²), C═CR¹ R², CHR¹ CHR², CR¹ ═CR², CHR¹ CR² ═CH, C.tbd.C,OCHR¹, CHR¹ O, CH(CF₃)O, CH(CN)O, OCHR¹ O, S(O)_(n) CHR¹, S(O)_(n) CHR¹O, CHR¹ S(O)_(n), CHR¹ OSO₂ NR⁴ CHR¹, CHR¹ NR⁴, CO₂, O₂ C, SO₂ O, OSO₂,CO.CO, COCHR¹, COCHR¹ O, CHR¹ CO, CHOH.CHR¹, CHR¹.CHOH, Ψ, Ω (for themeaning of Ψ and Ω see under "Chemical Formulae" later), CONR⁴, OCONR⁴,NR⁴ CO, CSNR⁴, OCS.NR⁴, SCO.NR⁴, NR⁴ CO₂, NR⁴ CS, NR⁴ CSO, NR⁴ COS, NR⁴CONR , S(O)_(n) NR⁴, NR⁴ S(O)_(n), Cs₂, S₂ C, CO.S, SCO, N═N, N═CR¹, CR¹═N, CHR¹ CHR² CH(OH), CHR¹ OCO, CHR¹ SCO, CHR¹ NR⁴ CO, CHR¹ NR⁴ CONR⁴,CHR¹ CHR² CO, O.N═CR¹, CHR¹ O.N═CR², CO.OCR¹ R², CHR¹ CHR² CHR³, OCHR¹CHR², (CH₂)_(m) O, CHR¹ OCHR², CHR¹ CHR² O, OCHR¹ CHR² O, S(O)_(n) CHR¹CHR², SCHR¹ CHR², CHR¹ S(O)_(n) CHR², CHR¹ CHR² S(O)_(n), CR¹ ═NNR⁴, CR¹═NO, NR⁴ N═CR¹, CHR¹ CONR², CHR¹ OCO.NR², CH═CHCH₂ O, C.tbd.CCH₂ O,COCHR¹ CHR² O, or (R⁵)₂ P⁺ CHR² Q⁻ ; where R¹, R² and R³, which may bethe same or different, are H, C₁₋₄ alkyl or phenyl; R⁴ is H, C₁₋₄ alkylor COR¹ ; R⁵ is optionally substituted phenyl; R⁶ is substituted phenyl;Q⁻ is a halide anion; n is 0, 1 or 2; and m is 3, 4 or 5.

The substituent Z in compound (I) is optionally substituted carbocyclylor optionally substituted heterocyclyl, this group being linked in eachcase to the group X through any of its atoms which valency allows. Wherevalency allows, each of the optionally substituted carbocyclyl orheterocyclyl groups can carry up to 5 substitutents.

The term "carbocyclyl" includes aromatic and non-aromatic rings such as,for example, phenyl, naphthyl, cyclopentyl, cyclohexyl and cyclohexenyl,the preferred value being phenyl.

The term "heterocyclyl" includes 5- and 6-membered aromatic andnon-aromatic heterocyclic rings containing one or more of each of theheteroatoms O, S and N (preferably S or N), fused benzenoid andheteroaromatic ring systems, and, in each case, the correspondingN-oxides; heteroaromatic ring systems are preferred. Examples ofheterocyclyl groups which Z may be are pyridinyl, pyrimidinyl,pyrazinyl, pyridazinyl, 1,2,3-, 1,2,4-, and 1,3,5-triazinyl,1,2,4,5-tetrazinyl, 1,2,3- and 1,2,4-triazolyl, thienyl, furyl,pyrrolyl, thiazolyl, purinyl, oxadiazolyl, quinolinyl, isoquinolinyl,quinoxalinyl, benzothienyl, benzoxazolyl, benzthiazolyl,tetrahydrofuryl, morpholinyl and piperidinyl and, where appropriate, thecorresponding N-oxides.

Substituents which may be present in the optionally substitutedcarbocyclyl and heterocyclyl moieties include one or more of thefollowing: halo, hydroxy, oxo, mercapto, C₁₋₄ alkyl (especially methyland ethyl), C₂₋₄ alkenyl (especially allyl), C₂₋₄ alkynyl (especiallypropargyl), C₁₋₄ alkoxy (especially methoxy), C₂₋₄ alkenyloxy(especially allyloxy), C₂₋₄ alkynyloxy (especially propargyloxy),halo(C₁₋₄)alkyl (especially trifluoromethyl), halo(C₁₋₄)alkoxy(especially trifluoromethoxy), C₁₋₄ alkylthio (especially methylthio),hydroxy(C₁₋₄)alkyl, C₁₋₄ alkoxy(C₁₋₄)-alkyl, C₃₋₆ cycloalkyl, C₃₋₆cycloalkyl(C₁₋₄)alkyl, optionally substituted aryl (especiallyoptionally substituted phenyl), optionally substituted heteroaryl(especially optionally substituted pyridinyl or pyrimidinyl), optionallysubstituted aryloxy (especially optionally substituted phenoxy),optionally substituted heteroaryloxy (especially optionally substitutedpyridinyloxy or pyrimidinyloxy), optionally substituted aryl(C₁₋₄ )alkyl(especially optionally substituted benzyl, optionally substitutedphenethyl and optionally substituted phenyl n-propyl) in which the alkylmoiety is optionally substituted with hydroxy, optionally substitutedheteroaryl(C₁₋₄)alkyl (especially optionally substituted pyridinyl- orpyrimidinyl(C₁₋₄)alkyl), optionally substituted aryl(C₂₋₄)alkenyl(especially optionally substituted phenylethenyl), optionallysubstituted heteroaryl(C₂₋₄)alkenyl (especially optionally substitutedpyridinylethenyl or pyrimidinylethenyl), optionally substitutedaryl(C₁₋₄ )alkoxy (especially optionally substitued benzyloxy),optionally substituted heteroaryl(C₁₋₄)-alkoxy (especially optionallysubstituted pyridinyl- or pyrimidinyl(C₁₋₄)-alkoxy), optionallysubstituted aryloxy(C₁₋₄)alkyl (especially phenoxy-methyl), optionallysubstituted heteroaryloxy(C₁₋₄)alkyl (especially optionally substitutedpyridinyloxy- or pyrimidinyloxy(C₁₋₄)alkyl), acyloxy, including C₁₋₄alkanoyloxy (especially acetyloxy) and benzoyloxy, cyano, thiocyanato,nitro, --NR'R", --NHCOR', --NHCONR'R", --CONR'R", --COOR', --OSO₂ R',--SO₂ R', --COR', --CR'═NR"or --N═CR'R" in which R' and R" areindependently hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ alkylthio, C₃₋₆cycloalkyl, C₃₋₆ cycloalkyl(C₁₋₄)alkyl, phenyl or benzyl, the phenyl andbenzyl groups being optionally substituted with halogen, C₁₋₄ alkyl orC₁₋₄ alkoxy. Or substituents, when ortho to one another, join to form a5- or 6-membered ring.

Substituents which may be present in the aryl or heteroaryl rings of anyof the foregoing substituents and in the phenyl ring of R⁵ and R⁶include one or more of the following: halo, hydroxy, mercapto, C₁₋₄alkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₁₋₄ alkoxy, C₂₋₄ alkenyloxy, C₂₋₄alkynyloxy, halo(C₁₋₄ )alkyl, halo(C₁₋₄ )alkoxy, C₁₋₄ alkylthio,hydroxy(C₁₋₄)alkyl, C₁₋₄ alkoxy(C₁₋₄)alkyl, C₃₋₆ cycloalkyl, C₃₋₆cycloalkyl(C₁₋₄)alkyl, alkanoyloxy, benzoyloxy, cyano, thiocyanato,nitro, --NR'R", --NHCOR', --NHCONR'R", --CONR'R", --COOR', --OSO₂ R',--SO₂ R', --COR', --CR'═NR" or --N═CR'R" in which R' and R" have themeanings given above.

In one aspect the invention includes compounds having the formula (I) inwhich K and M are both nitrogen; L is CH; Z is optionally substitutedphenyl and X is as defined above. Suitably X is S, CH₂ O, CH₂ S, CH₂ CH₂O or CH₂ CH₂ CH₂ O.

In a particular aspect the invention includes a compound having theformula (I.1) in which Z is phenyl optionally substituted with halo,C₁₋₄ alkyl or trifluoromethyl; and X is S, CH₂ O, CH₂ S, CH₂ CH₂ O, CH₂CH₂ CH₂ O or (E) --CH═NO.

In another particular aspect the invention includes a compound havingthe formula (I.2) in which Z is phenyl optionally substituted with C₁₋₄alkyl; X is S; and A is H or Cl.

The invention is illustrated by the compounds listed in Tables I to VIwhich follow. The compounds of Tables I to VI have the formulae (I.3) to(I.8), respectively, in which the values of Z and X are given in TablesI and III to VI and the values of Z, X and A are given in Table II.Throughout the Tables the methyl 3-methoxypropenoate group has the(E)-configuration.

                  TABLE I                                                         ______________________________________                                        (Formula (I.3))                                                               Compound                                                                      No       Z                X                                                   ______________________________________                                        1        C.sub.6 H.sub.5  S                                                   2        C.sub.6 H.sub.5  SO                                                  3        C.sub.6 H.sub.5  SO.sub.2                                            4        C.sub.6 H.sub.5  NH                                                  5        C.sub.6 H.sub.5  NCH.sub.3                                           6        C.sub.6 H.sub.5  NCH.sub.2 CH.sub.3                                  7        C.sub.6 H.sub.5  NCOCH.sub.3                                         8        C.sub.6 H.sub.5  NCH(CH.sub.3).sub.2                                 9        C.sub.6 H.sub.5  CH.sub.2                                            10       C.sub.6 H.sub.5  CH(CH.sub.3)                                        11       C.sub.6 H.sub.5  C(CH.sub.3).sub.2                                   12       C.sub.6 H.sub.5  CO                                                  13       C.sub.6 H.sub.5  C ═ CH.sub.2                                    14       C.sub.6 H.sub.5  C ═ C(CH.sub.3).sub.2                           15       C.sub.6 H.sub.5  CH.sub.2 CH.sub.2                                   16       C.sub.6 H.sub.5  CH(CH.sub.3)CH.sub.2                                17       C.sub.6 H.sub.5  CH.sub.2 CH(CH.sub.3)                               18       C.sub.6 H.sub.5  (E)-CH ═ CH                                     19       C.sub.6 H.sub.5  (E)-C(CH.sub.3) ═ C(CH.sub.3)                   20       C.sub.6 H.sub.5  C.tbd.C                                             21       C.sub.6 H.sub.5  OCH.sub.2                                           22       C.sub.6 H.sub.5  OCH(CH.sub.3)                                       23       C.sub.6 H.sub.5  CH.sub.2 O                                          24       C.sub.6 H.sub.5  CH(CH.sub.3)O                                       25       C.sub.6 H.sub.5  SCH.sub.2                                           26       C.sub.6 H.sub.5  SCH(CH.sub.3)                                       27       C.sub.6 H.sub.5  S(O)CH.sub.2                                        28       C.sub.6 H.sub.5  S(O)CH(CH.sub.3)                                    29       C.sub.6 H.sub.5  S(O).sub.2 CH.sub.2                                 30       C.sub.6 H.sub.5  S(O).sub.2 CH(CH.sub.3)                             31       C.sub.6 H.sub.5  CH.sub.2 S                                          32       C.sub.6 H.sub.5  CH(CH.sub.3)S                                       33       C.sub.6 H.sub.5  CH.sub.2 S(O)                                       34       C.sub.6 H.sub.5  CH(CH.sub.3)S(O)                                    35       C.sub.6 H.sub.5  CH.sub.2 S(O).sub.2                                 36       C.sub.6 H.sub.5  CH(CH.sub.3)S(O).sub.2                              37       C.sub.6 H.sub.5  NHCH.sub.2                                          38       C.sub.6 H.sub.5  N(CH.sub.3)CH.sub.2                                 39       C.sub.6 H.sub.5  N(COCH.sub.3)CH.sub.2                               40       C.sub.6 H.sub.5  NHCH(CH.sub.3)                                      41       C.sub.6 H.sub.5  N(CH.sub.3)CH(CH.sub.3)                             42       C.sub.6 H.sub.5  N(COCH.sub.3)CH(CH.sub.3)                           43       C.sub.6 H.sub.5  CH.sub.2 NH                                         44       C.sub.6 H.sub.5  CH.sub.2 N(CH.sub.3)                                45       C.sub.6 H.sub.5  CH.sub.2 N(COCH.sub.3)                              46       C.sub.6 H.sub.5  CH(CH.sub.3)NH                                      47       C.sub.6 H.sub.5  CH(CH.sub.3)N(CH.sub.3)                             48       C.sub.6 H.sub.5  CH(CH.sub.3)N(COCH.sub.3)                           49       C.sub.6 H.sub.5  CO.sub.2                                            50       C.sub.6 H.sub.5  O.sub.2 C                                           51       C.sub.6 H.sub.5  SO.sub.2 O                                          52       C.sub.6 H.sub.5  OSO.sub.2                                           53       C.sub.6 H.sub.5  CO.CO                                               54       C.sub.6 H.sub.5  COCH.sub.2                                          55       C.sub.6 H.sub.5  COCH(CH.sub.3)                                      56       C.sub.6 H.sub.5  CH.sub.2 CO                                         57       C.sub.6 H.sub.5  CH(CH.sub.3)CO                                      58       C.sub.6 H.sub.5  CH(OH)CH.sub.2                                      59       C.sub.6 H.sub.5  CH(OH)CH(CH.sub.3)                                  60       C.sub.6 H.sub.5  CH.sub.2 CH(OH)                                     61       C.sub.6 H.sub.5  CH(CH.sub.3)CH(OH)                                  62       C.sub.6 H.sub.5  CONH                                                63       C.sub.6 H.sub.5  CON(CH.sub.3)                                       64       C.sub.6 H.sub.5  CON(CH.sub.2 CH.sub.2 CH.sub.3)                     65       C.sub.6 H.sub.5  CON(CHO)                                            66       C.sub.6 H.sub.5  CON(COCH.sub.3)                                     67       C.sub.6 H.sub.5  NHCO                                                68       C.sub.6 H.sub.5  N(CH.sub.3)CO                                       69       C.sub.6 H.sub.5  N(CH.sub.2 CH.sub.3)CO                              70       C.sub.6 H.sub.5  N(CHO)CO                                            71       C.sub.6 H.sub.5  N(COCH.sub.3)CO                                     72       C.sub.6 H.sub.5  CSN(CH.sub.3)                                       73       C.sub.6 H.sub.5  CSNH                                                74       C.sub.6 H.sub.5  NHCS                                                75       C.sub.6 H.sub.5  N(CH.sub.3)CS                                       76       C.sub.6 H.sub.5  SO.sub.2 NH                                         77       C.sub.6 H.sub.5  SO.sub.2 N(CH.sub.3)                                78       C.sub.6 H.sub.5  NHSO.sub.2                                          79       C.sub.6 H.sub.5  N(CH.sub.3)SO.sub.2                                 80       C.sub.6 H.sub.5  N(CH.sub.2 CH.sub.3)SO.sub.2                        81       C.sub.6 H.sub.5  CS.sub.2                                            82       C.sub.6 H.sub.5  S.sub.2 C                                           83       C.sub.6 H.sub.5  COS                                                 84       C.sub.6 H.sub.5  SCO                                                 85       C.sub.6 H.sub.5  (E)-N ═ N                                       86       C.sub.6 H.sub.5  (E)-N ═ CH                                      87       C.sub.6 H.sub.5  (E)-N ═ C(CH.sub.3)                             88       C.sub.6 H.sub.5  (E)-CH ═ N                                      89       C.sub.6 H.sub.5  (E)-C(CH.sub.3) ═ N                             90       C.sub.6 H.sub.5  CH.sub.2 CH.sub.2 CH.sub.2                          91       C.sub.6 H.sub.5  CH(CH.sub.3)CH.sub.2 CH.sub.2                       92       C.sub.6 H.sub.5  CH.sub.2 CH(CH.sub.3)CH.sub.2                       93       C.sub.6 H.sub.5  CH.sub.2 CH.sub.2 CH(CH.sub.3)                      94       C.sub.6 H.sub.5  OCH.sub.2 CH.sub.2                                  95       C.sub.6 H.sub.5  CH.sub.2 OCH.sub.2                                  96       C.sub.6 H.sub.5  CH.sub.2 CH.sub.2 O                                 97       C.sub.6 H.sub.5  SCH.sub.2 CH.sub.2                                  98       C.sub.6 H.sub.5  S(O)CH.sub.2 CH.sub.2                               99       C.sub.6 H.sub.5  S(O).sub.2 CH.sub.2 CH.sub.2                        100      C.sub.6 H.sub.5  CH.sub.2 SCH.sub.2                                  101      C.sub.6 H.sub.5  CH.sub.2 S(O)CH.sub.2                               102      C.sub.6 H.sub.5  CH.sub.2 S(O).sub.2 CH.sub.2                        103      C.sub.6 H.sub.5  CH.sub.2 CH.sub.2 S                                 104      C.sub.6 H.sub.5  CH.sub.2 CH.sub.2 S(O)                              105      C.sub.6 H.sub.5  CH.sub.2 CH.sub.2 S(O).sub.2                        106      C.sub.6 H.sub.5  (E)-CH ═ NNH                                    107      C.sub.6 H.sub.5  (E)-C(CH.sub.3) ═ NNH                           108      C.sub.6 H.sub.5  (E)-CH ═ NN(CH.sub.3)                           109      C.sub.6 H.sub.5  (E)-NHN ═ CH                                    110      C.sub.6 H.sub.5  (E)-NHN ═ C(CH.sub.3)                           111      C.sub.6 H.sub.5  (E)-N(CH.sub.3)N ═ CH                           112      C.sub.6 H.sub.5  CH.sub.2 CONH                                       113      C.sub.6 H.sub.5  CH(CH.sub.3)CON(CH.sub.3)                           114      C.sub.6 H.sub.5  CH(CH.sub.3)CON(CH.sub.3)                           115      C.sub.6 H.sub.5  (E)-CH ═ CHCH.sub.2 O                           116      C.sub.6 H.sub.5  COCH.sub.2 CH.sub.2 O                               117      C.sub.6 H.sub.5  *                                                   118      C.sub.6 H.sub.5  *                                                   119      2-Cl--C.sub.6 H.sub.4                                                                          S                                                   120      3-Cl--C.sub.6 H.sub.4                                                                          N(CH.sub.3)                                         121      4-Cl--C.sub.6 H.sub.4                                                                          NH                                                  122      2-F--C.sub.6 H.sub.4                                                                           OCH.sub.2                                           123      3-F--C.sub.6 H.sub.4                                                                           CH.sub.2 O                                          124      4-F--C.sub.6 H.sub.4                                                                           S                                                   125      2-CH.sub.3 --C.sub.6 H.sub.4                                                                   N(CH.sub.3)                                         126      3-CH.sub.3 --C.sub.6 H.sub.4                                                                   CH.sub.2                                            127      4-CH.sub.3 --C.sub.6 H.sub.4                                                                   OCH.sub.2                                           128      2-CH.sub.3 O--C.sub.6 H.sub.4                                                                  CH.sub.2 O                                          129      3-CH.sub.3 O--C.sub.6 H.sub.4                                                                  S                                                   130      4-CH.sub.3 O--C.sub.6 H.sub.4                                                                  N(CH.sub.3)                                         131      2-NO.sub.2 --C.sub.6 H.sub.4                                                                   NH                                                  132      3-NO.sub.2 --C.sub.6 H.sub.4                                                                   OCH.sub.2                                           133      4-F--C.sub.6 H.sub.4                                                                           CH.sub.2 O                                          134      2-Cyano-C.sub.6 H.sub.4                                                                        S                                                   135      3-Cyano-C.sub.6 H.sub.4                                                                        N(CH.sub.3)                                         136      4-Cyano-C.sub.6 H.sub.4                                                                        CH.sub.2                                            137      2-Br--C.sub.6 H.sub.4                                                                          OCH.sub.2                                           138      3-Br--C.sub.6 H.sub.4                                                                          CH.sub.2 O                                          139      4-Br--C.sub.6 H.sub.4                                                                          S                                                   140      2-CF.sub.3 --C.sub.6 H.sub.4                                                                   N(CH.sub.3)                                         141      3-CF.sub.3 --C.sub.6 H.sub.4                                                                   NH                                                  142      4-CF.sub.3 --C.sub.6 H.sub.4                                                                   OCH.sub.2                                           143      2-C.sub.6 H.sub.5 O--C.sub.6 H.sub.4                                                           CH.sub.2 O                                          144      3-C.sub.6 H.sub.5 O--C.sub.6 H.sub.4                                                           S                                                   145      4-C.sub.6 H.sub.5 O--C.sub.6 H.sub.4                                                           N(CH.sub.3)                                         146      2-CH.sub.3 CH.sub.2 O--C.sub.6 H.sub.4                                                         CH.sub.2                                            147      3-CH.sub.3 CH.sub.2 O--C.sub.6 H.sub.4                                                         OCH.sub.2                                           148      4-CH.sub.3 CH.sub.2 O--C.sub.6 H.sub.4                                                         CH.sub.2 O                                          149      2-C.sub.6 H.sub.5 --C.sub.6 H.sub.4                                                            S                                                   150      3-C.sub.6 H.sub.5 --C.sub.6 H.sub.4                                                            N(CH.sub.3)                                         151      4-C.sub.6 H.sub.5 --C.sub.6 H.sub.4                                                            NH                                                  152      2,3-di-Cl--C.sub.6 H.sub.3                                                                     OCH.sub.2                                           153      2,4-di-Cl--C.sub.6 H.sub.3                                                                     CH.sub.2 O                                          154      2,5-di-Cl--C.sub.6 H.sub.3                                                                     S                                                   155      2,6-di-Cl--C.sub.6 H.sub.3                                                                     N(CH.sub.3)                                         156      3,4-di-Cl--C.sub.6 H.sub.3                                                                     CH.sub.2                                            157      3,5-di-Cl--C.sub.6 H.sub.3                                                                     OCH.sub.2                                           158      2-Cl-3-CH.sub.3 O--C.sub.6 H.sub.3                                                             CH.sub.2 O                                          159      2-Cl-4-CH.sub.3 O--C.sub.6 H.sub.3                                                             S                                                   160      2-Cl-5-CH.sub.3 O--C.sub.6 H.sub.3                                                             N(CH.sub.3)                                         161      2-Cl-6-CH.sub.3 O--C.sub.6 H.sub.3                                                             NH                                                  162      3-Cl-4-CH.sub.3 O--C.sub.6 H.sub.3                                                             OCH.sub.2                                           163      3-Cl-5-CH.sub.3 O--C.sub.6 H.sub.3                                                             CH.sub.2 O                                          164      2-CH.sub.3 O-3-Cl--C.sub.6 H.sub.3                                                             S                                                   165      2-CH.sub.3 O-4-Cl--C.sub.6 H.sub.3                                                             N(CH.sub.3)                                         166      2-CH.sub.3 O-5-Cl--C.sub.6 H.sub.3                                                             CH.sub.2                                            167      3-CH.sub.3 O-4-Cl--C.sub.6 H.sub.3                                                             OCH.sub.2                                           168      1-Naphthyl       CH.sub.2 O                                          169      2-Naphthyl       S                                                   170      2-(E)-(CH.sub.3 O.sub.2 C.                                                                     N(CH.sub.3)                                                  C ═ CH.OCH.sub.3)C.sub.6 H.sub.4                                 171      2-(E)-(CH.sub.3 O.sub.2 C.                                                                     NH                                                           C ═ CH.OCH.sub.3)C.sub.6 H.sub.4                                 172      2-(E)-(CH.sub.3 O.sub.2 C.                                                                     OCH.sub.2                                                    C ═ CH.OCH.sub.3)C.sub.6 H.sub.4                                 173      2-(E)-(CH.sub.3 O.sub.2 C.                                                                     CH.sub.2 O                                                   C ═ CH.OCH.sub.3)C.sub.6 H.sub.4                                 174      2-(E)-(CH.sub.3 O.sub.2 C.                                                                     S                                                            C ═ CH.OCH.sub.3)C.sub.6 H.sub.4                                 175      C.sub.6 F.sub.5  N(CH.sub.3)                                         176      2,6-di-F--C.sub.6 H.sub.3                                                                      CH.sub.2                                            177      2-Cyano-6-F--C.sub.6 H.sub.3                                                                   OCH.sub.2                                           178      3-Cyano-4,6-di-F--C.sub.6 H.sub.2                                                              CH.sub.2 O                                          179      2,6-di-Cyano-C.sub.6 H.sub.3                                                                   S                                                   180      Pyridin-2-yl     S                                                   181      Pyridin-2-yl     N(CH.sub.3)                                         182      Pyridin-2-yl     NH                                                  183      Pyridin-2-yl     OCH.sub.2                                           184      Pyridin-2-yl     CH.sub.2 O                                          185      Pyridin-2-yl     CH.sub.2 CH.sub.2 O                                 186      Pyridin-2-yl     CH.sub.2 CH.sub.2 CH.sub.2 O                        187      Pyridin-3-yl     S                                                   188      Pyridin-3-yl     N(CH.sub.3)                                         189      Pyridin-3-yl     NH                                                  190      Pyridin-3-yl     OCH.sub.2                                           191      Pyridin-3-yl     CH.sub.2 O                                          192      Pyridin-3-yl     CH.sub.2 CH.sub.2 O                                 193      Pyridin-3-yl     CH.sub.2 CH.sub.2 CH.sub.2 O                        194      Pyridin-4-yl     S                                                   195      Pyridin-4-yl     N(CH.sub.3)                                         196      Pyridin-4-yl     NH                                                  197      Pyridin-4-yl     OCH.sub.2                                           198      Pyridin-4-yl     CH.sub.2 O                                          199      Pyridin-4-yl     CH.sub.2 CH.sub.2 O                                 200      Pyridin-4-yl     CH.sub.2 CH.sub.2 CH.sub.2 O                        201      Pyrimidin-2-yl   S                                                   202      Pyrimidin-2-yl   N(CH.sub.3)                                         203      Pyrimidin-2-yl   NH                                                  204      Pyrimidin-2-yl   OCH.sub.2                                           205      Pyrimidin-2-yl   CH.sub.2 O                                          206      Pyrimidin-2-yl   CH.sub.2 CH.sub.2 O                                 207      Pyrimidin-2-yl   CH.sub.2 CH.sub.2 CH.sub.2 O                        208      Pyrimidin-4-yl   S                                                   209      Pyrimidin-4-yl   N(CH.sub.3)                                         210      Pyrimidin-4-yl   NH                                                  211      Pyrimidin-4-yl   OCH.sub.2                                           212      Pyrimidin-4-yl   CH.sub.2 O                                          213      Pyrimidin-4-yl   CH.sub.2 CH.sub.2 O                                 214      Pyrimidin-4-yl   CH.sub.2 CH.sub.2 CH.sub.2 O                        215      Pyrimidin-5-yl   S                                                   216      Pyrimidin-5-yl   N(CH.sub.3)                                         217      Pyrimidin-5-yl   NH                                                  218      Pyrimidin-5-yl   OCH.sub.2                                           219      Pyrimidin-5-yl   CH.sub.2 O                                          220      Pyrimidin-5-yl   CH.sub.2 CH.sub.2 O                                 221      Pyrimidin-5-yl   CH.sub.2 CH.sub.2 CH.sub.2 O                        222      Pyrazin-2-yl     S                                                   223      Pyrazin-2-yl     N(CH.sub.3)                                         224      Pyrazin-2-yl     NH                                                  225      Pyrazin-2-yl     OCH.sub.2                                           226      Pyrazin-2-yl     CH.sub.2 O                                          227      Pyrazin-2-yl     CH.sub.2 CH.sub.2 O                                 228      Pyrazin-2-yl     CH.sub.2 CH.sub.2 CH.sub.2 O                        229      Pyridazin-3-yl   S                                                   230      Pyridazin-3-yl   N(CH.sub.3)                                         231      Pyridazin-3-yl   NH                                                  232      Pyridazin-3-yl   OCH.sub.2                                           233      Pyridazin-3-yl   CH.sub.2 O                                          234      Pyridazin-3-yl   CH.sub.2 CH.sub.2 O                                 235      Pyridazin-3-yl   CH.sub.2 CH.sub.2 CH.sub.2 O                        236      Pyridazin-4-yl   S                                                   237      Pyridazin-4-yl   N(CH.sub.3)                                         238      Pyridazin-4-yl   NH                                                  239      Pyridazin-4-yl   OCH.sub.2                                           240      Pyridazin-4-yl   CH.sub.2 O                                          241      Pyridazin-4-yl   CH.sub.2 CH.sub.2 O                                 242      Pyridazin-4-yl   CH.sub.2 CH.sub.2 CH.sub.2 O                        243      1,2,4-Triazin-3-yl                                                                             S                                                   244      1,2,4-Triazin-3-yl                                                                             N(CH.sub.3)                                         245      1,2,4-Triazin-5-yl                                                                             NH                                                  246      1,2,4-Triazin-5-yl                                                                             OCH.sub.2                                           247      1,2,4-Triazin-6-yl                                                                             CH.sub.2 O                                          248      1,2,4-Triazin-6-yl                                                                             CH.sub.2 CH.sub.2 O                                 249      1,3,5-Triazin-2-yl                                                                             CH.sub.2 CH.sub.2 CHO                               250      1,3,5-Triazin-2-yl                                                                             S                                                   251      1,3,5-Triazin-2-yl                                                                             N(CH.sub.3)                                         252      Quinolin-2-yl    NH                                                  253      Quinolin-2-yl    OCH.sub.2                                           254      Quinolin-2-yl    CH.sub.2 O                                          255      Isoquinolin-1-yl CH.sub.2 CH.sub.2 O                                 256      Isoquinolin-1-yl CH.sub.2 CH.sub.2 CH.sub.2 O                        257      Isoquinolin-1-yl S                                                   258      Benzoxazol-2-yl  N(CH.sub.3)                                         259      Benzoxazol-2-yl  NH                                                  260      Benzoxazol-2-yl  OCH.sub.2                                           261      Benzthiazol-2-yl CH.sub.2 O                                          262      Benzthiazol-2-yl CH.sub.2 CH.sub.2 O                                 263      Benzthiazol-2-yl CH.sub.2 CH.sub.2 CH.sub.2 O                        264      Thien-2-yl       S                                                   265      Thien-2-yl       N(CH.sub.3)                                         266      Thien-2-yl       NH                                                  267      Thien-3-yl       OCH.sub.2                                           268      Thien-3-yl       CH.sub.2 O                                          269      Thien-3-yl       CH.sub.2 CH.sub.2 O                                 270      1,2,4-Triazol-1-yl                                                                             CH.sub.2 CH.sub.2 CH.sub.2 O                        271      Quinazolin-4-yl  S                                                   272      Quinazolin-4-yl  N(CH.sub.3)                                         273      Quinolin-4-yl    NH                                                  274      Quinolin-4-yl    OCH.sub.2                                           275      Purin-6-yl       CH.sub.2 O                                          276      Thiazol-2-yl     CH.sub.2 CH.sub.2 O                                 277      Thiazol-2-yl     CH.sub.2 CH.sub.2 CH.sub.2 O                        278      Thiazol-4-yl     S                                                   279      Thiazol-4-yl     N(CH.sub.3)                                         280      Thiazol-5-yl     NH                                                  281      Thiazol-5-yl     OCH.sub.2                                           282      Furan-2-yl       CH.sub.2 O                                          283      N--CH.sub.3 -Pyrrol-2-yl                                                                       CH.sub.2 CH.sub.2 O                                 284      N--CH.sub.3 -Pyrrol-2-yl                                                                       CH.sub.2 CH.sub.2 CH.sub.2 O                        285      5-CF.sub.3 -Pyridin-2-yl                                                                       S                                                   286      3-F-Pyridin-2-yl N(CH.sub.3)                                         287      3-Cl-Pyridin-2-yl                                                                              NH                                                  288      4-Br-Pyridin-2-yl                                                                              OCH.sub.2                                           289      3-CH.sub.3 -Pyridin-2-yl                                                                       CH.sub.2 O                                          290      6-CH.sub.3 O-Pyridin-2-yl                                                                      CH.sub.2 CH.sub.2 O                                 291      4,6-di-F-Pyridin-2-yl                                                                          CH.sub.2 CH.sub.2 CH.sub.2 O                        292      2-Cl-Pyridin-3-yl                                                                              S                                                   293      2-CH.sub.3 O-Pyridin-3-yl                                                                      N(CH.sub.3)                                         294      2-Cl-Pyridin-4-yl                                                                              NH                                                  295      4-Cl-Pyrimidin-2-yl                                                                            OCH.sub.2                                           296      4-Cyano-Pyrimidin-2-yl                                                                         CH.sub.2 O                                          297      4-CH.sub.3 -Pyrimidin-2-yl                                                                     CH.sub.2 CH.sub.2 O                                 298      5-CH.sub.3 -Pyrimidin-2-yl                                                                     CH.sub.2 CH.sub.2 CH.sub.2 O                        299      5-Cyano-pyrimidin-2-yl                                                                         S                                                   300      5-F-Pyrimidin-2-yl                                                                             N(CH.sub.3)                                         301      2-Cl-Pyrimidin-4-yl                                                                            NH                                                  302      2-CH.sub.3 -Pyrimidin-4-yl                                                                     OCH.sub.2                                           303      2-CH.sub.3 S-Pyrimidin-4-yl                                                                    CH.sub.2 O                                          304      6-Cl-Pyrazin-2-yl                                                                              CH.sub.2 CH.sub.2 O                                 305      6-Cl-Pyridazin-3-yl                                                                            CH.sub.2 CH.sub.2 CH.sub.2 O                        306      6-Cl-Pyridazin-3-yl                                                                            S                                                   307      2-CH.sub.3 -Thiazol-4-yl                                                                       N(CH.sub.3)                                         308      5-CF.sub.3 -1,3,4-Thiadiazol-2-yl                                                              NH                                                  309      4-Cl-1,2,5-Thiadiazol-3-yl                                                                     OCH.sub.2                                           310      Pyrimidin-2-yl,N-oxide                                                                         CH.sub.2 O                                          311      Pyrimidin-4-yl,1-N-oxide                                                                       CH.sub.2 CH.sub.2 O                                 312      Pyrimidin-4-yl,3-N-oxide                                                                       CH.sub.2 CH.sub.2 CH.sub.2 O                        313      Pyridin-2-yl,N-oxide                                                                           S                                                   314      Pyrazin-2-yl,1-N-oxide                                                                         N(CH.sub.3)                                                                   NH                                                  315      *                                                                    316      2-Cyano-C.sub.6 H.sub.4                                                                        N(CH.sub.3)                                         317      Pyridin-2-yl     SO                                                  318      Pyridin-2-yl     SO.sub.2                                            319      2-Cyano-C.sub.6 H.sub.4                                                                        CH.sub.2 CH.sub.2 O                                 320      2-NO.sub.2 --C.sub.6 H.sub.4                                                                   CH.sub.2 CH.sub.2 O                                 321      4-Cyano-C.sub.6 H.sub.4                                                                        CH.sub.2 CH.sub.2 O                                 322      C.sub.6 H.sub.5  CH.sub.2 CH.sub.2 CH.sub.2 O                        323      2-NO.sub.2 --C.sub.6 H.sub.4                                                                   CH.sub.2 CH.sub.2 CH.sub.2 O                        324      2-HO--C.sub.6 H.sub.4                                                                          CONH                                                325      2-CF.sub.3 --C.sub.6 H.sub.4                                                                   CH.sub.2 CH.sub.2 O                                 326      2-CH.sub.3 --C.sub.6 H.sub.4                                                                   CH.sub.2 CH.sub.2 O                                 327      2-CH.sub.3 O--C.sub.6 H.sub.4                                                                  CH.sub.2 CH.sub.2 O                                 328      2-F--C.sub.6 H.sub.4                                                                           CH.sub.2 CH.sub.2 O                                 329      2-HO--C.sub.6 H.sub.4                                                                          CSNH                                                330      2-Cl--C.sub.6 H.sub.4                                                                          CH.sub.2 CH.sub.2 O                                 331      C.sub.6 H.sub.5  CH(CN)O                                             332      2,6-di-F--C.sub.6 H.sub.3                                                                      CH.sub.2 CH.sub.2 O                                 333      C.sub.6 H.sub.5  CH(CF.sub.3)O                                       334      2-Cl-6-F--C.sub.6 H.sub.3                                                                      CH.sub.2 CH.sub.2 O                                 335      2,6-di-Cl--C.sub.6 H.sub.3                                                                     CH.sub.2 CH.sub.2 O                                 336      2,6-di-F--C.sub.6 H.sub.3                                                                      CH.sub.2 O                                          337      2-NO.sub.2 --C.sub.6 H.sub.4                                                                   CH.sub.2 O                                          338      C.sub.6 H.sub.5  (E)-CH ═ CHCH.sub.2 O                           339      2-Cyano-C.sub.6 H.sub.4                                                                        NH                                                  340      2-HO--C.sub.6 H.sub.4                                                                          NH                                                  341      2-(CH.sub.3 O)-C.sub.6 H.sub.4                                                                 NH                                                  342      2-Cyano-C.sub.6 H.sub.4                                                                        SO.sub.2 O                                          343      2,6-di-F--C.sub.6 H.sub.4                                                                      OCH.sub.2 CH.sub.2 O                                344      2-Cl-6-CF.sub.3 --C.sub.6 H.sub.3                                                              CH.sub.2 O                                          345      2-Cl--C.sub.6 H.sub.4                                                                          CH.sub.2 CH.sub.2 CH.sub.2 O                        346      2-CF.sub.3 --C.sub.6 H.sub.4                                                                   CH.sub.2 O                                          347      2-F-6-Cl--C.sub.6 H.sub.3                                                                      CH.sub.2 O                                          348      C.sub.6 H.sub.5  C.tbd.CCH.sub.2 O                                   349      C.sub.6 F.sub.5  CH.sub.2 O                                          350      2-Cyano-C.sub.6 H.sub.4                                                                        CH.sub.2 O                                          351      4-Cyano-C.sub.6 H.sub.4                                                                        OCH.sub.2 CH.sub.2 O                                352      C.sub.6 H.sub.5  SCH.sub.2 CH.sub.2 O                                353      2-HO--C.sub.6 H.sub.4                                                                          N(CHO)                                              354      2-Cyano-C.sub.6 H.sub.4                                                                        SCH.sub.2 CH.sub.2 O                                355      2-Thienyl        CH.sub.2 O                                          356      2-Cyano-C.sub.6 H.sub.4                                                                        (E)-CH ═ CHCH.sub.2 O                           357      2-Cyano-C.sub.6 H.sub.4                                                                        OCH.sub.2 CH.sub.2 O                                358      2-Cyano-6-F-C.sub.6 H.sub.3                                                                    OCH.sub.2 CH.sub.2 O                                359      C.sub.6 H.sub.5  CON(COC.sub.6 H.sub.5)                              360      2-CH.sub.3 --C.sub.6 H.sub.4                                                                   S                                                   361      3-CF.sub.3 --C.sub.6 H.sub.4                                                                   (E)-CH ═ NO                                     362      Pyrrol-2-yl      (E)-C(CH.sub.3) ═ NO                            ______________________________________                                         * For these values of Z and X see under "Chemical Formulae" later.       

Table II comprises 362 compounds of the formula (I.4) with all thevalues of X and Z listed in Table I and with the value of A beinghydrogen except where otherwise shown. That is, compounds numbers 1 to362 of Table II are the same as those of Table I except that the 3- and5-substituents of the 1,2,4-triazine ring in Table I are reversed inTable II and compound number 360A of Table II has an additionalsubstituent in the triazine ring.

                  TABLE II                                                        ______________________________________                                        (Formula I.4)                                                                 Compound                              Melting                                 No.      Z         X      A    Olefinic.sup.+                                                                       Point (° C.)                     ______________________________________                                        360      2-CH.sub.3 --C.sub.6 H.sub.4                                                            S      H    7.47   Gum                                     360A     2-CH.sub.3 --C.sub.6 H.sub.4                                                            S      Cl   7.49   Gum                                     ______________________________________                                    

Table III comprises 362 compounds of the formula (I.5) with all thevalues of X and Z listed in Table I. That is, compounds numbers 1 to 362of Table III are the same as those of Table I except that the triazinering is a 3,5-disubstituted 1,2,4-triazine in Table I and a 2,4-disubstituted 1,3,5-triazine in Table III.

                  TABLE III                                                       ______________________________________                                        (Formula I.5)                                                                 Compound                             Melting                                  No.     Z         X           Olefinic.sup.+                                                                       Point (° C.)                      ______________________________________                                        1       C.sub.6 H.sub.5                                                                         S           7.39   119-121                                  23      C.sub.6 H.sub.5                                                                         CH.sub.2 O  7.45   Gum                                      31      C.sub.6 H.sub.5                                                                         CH.sub.2 S  7.46   Gum                                      96      C.sub.6 H.sub.5                                                                         CH.sub.2 CH.sub.2 O                                                                       7.46   Gum                                      133     4-F--C.sub.6 H.sub.4                                                                    CH.sub.2 O  7.46   Gum                                      322     C.sub.6 H.sub.5                                                                         CH.sub.2 CH.sub.2 CH.sub.2 O                                                              7.46   Gum                                      360     2-CH.sub.3 --C.sub.6 H.sub.4                                                            S           7.47   112-114                                  361     3-CF.sub.3 --C.sub.6 H.sub.4                                                            (E)-CH ═NO                                                                            7.50   127-131                                  362     Pyrrol-2-yl                                                                             (E)-C(CH.sub.3) ═NO                                                                   7.48   Gum                                      ______________________________________                                    

Table IV comprises 362 compounds of the formula ( I.6) with all thevalues of X and Z listed in Table I. That is, compounds numbers 1 to 362of Table IV are the same as those of Table I except that the triazinering is an 0-linked 3,5-disubstituted 1,2,4-triazine in Table I and aS-linked 3,5-disubstituted 1,2,4-triazine in Table IV.

Table V comprises 362 compounds of the formula (I.7) with all the valuesof X and Z listed in Table I. That is, compounds numbers 1 to 362 ofTable V are the same as those of Table I except that the triazine ringis an 0-linked 3,5-disubstituted 1,2,4-triazine in Table I and aS-linked 3,5-disubstituted 1,2,5-triazine in Table V.

Table VI comprises 362 compounds of the formula (I.8) with all thevalues of X and Z listed in Table I. That is, compounds numbers 1 to 362of Table VI are the same as those of Table I except that the triazinering is an 0-linked 3,5-disubstituted 1,2,4-triazine in Table I and aS-linked 2,4-disubstituted 1,3,5-triazine in Table VI.

TABLE VII Selected Proton NMR Data

Table VII shows selected proton NMR data for compounds described inTable III. As already indicated, chemical shifts are measured in ppmfrom tetramethylsilane and deuterochloroform was used as solvent. TheNMR instrument operated at a frequency of 270 MHz. The followingabbreviations are used:

    ______________________________________                                        Compound                                                                      No                                                                            (of Table III)                                                                        Proton NMR data                                                       ______________________________________                                        1       3.53(3H,s); 3.65(3H,s); 6.98-7.07(1H,m); 7.16-7.36                            (6H,m); 7.39(1H,s); 7.42-7.50(2H,m); 8.46(1H,s) ppm.                  23      3.58(3H,s); 3.66(3H,s); 5.37(2H,s); 7.17-7.43(9H,m);                          7.45(1H,s); 8.61(1H,s) ppm.                                           31      3.58(3H,s); 3.65(3H,s); 4.23(2H,s); 7.13-7.27(5H,m);                          7.28-7.45(3H,m); 7.46(1H,s); 8.56(1H,s) ppm.                          96      3.04(2H,t); 3.58(3H,s); 3.70(3H,s); 4.52(2H,t);                               7.46(1H,s); 8.60(1H,s) ppm.                                           133     3.57(3H,s); 3.68(3H,s); 5.31(2H,s); 6.95(2H,t);                               7.2-7.5(6H,m); 7.46(1H,s); 8.61(1H,s) ppm.                            322     2.09(2H,m); 2.75(2H,t); 3.60(3H,s); 3.72(3H,s);                               4.36(2H,t); 7.46(1H,s); 8.60(1H,s); ppm.                              362     2.40(3H,s); 3.61(3H,s); 3.74(3H,s); 6.25-6.29(1H,m);                          6.66(1H,br s); 6.95(1H,br s); 7.20-7.45(4H,m); 7.48(1H,s);                    8.70(1H,s); 9.77(1H,br s) ppm.                                        ______________________________________                                         br = broad                                                                    s = singlet                                                                   d = doublet                                                                   t = triplet                                                                   q = quartet                                                                   m = multiplet                                                                 ppm = parts per million                                                  

The compounds of the invention of formula (I) equivalent to (IA) when Wis the group CH₃ O₂ C.C═CH.OCH₃ and Z¹ is Z; and equivalent to (IB) whenW is the group CH₃ O₂ C.C═CH.OCH₃ ! can be prepared by the steps shownin Schemes I and II. In these Schemes, K, L, M, Z, T and X, are asdefined above; Z¹ is Z or a group which can be converted by standardprocedures described in the chemical literature into Z; W is CH₃ O₂C.C═CH.OCH₃ or a group that can be transformed into CH₃ O₂ C.C═CH.OCH₃using methods previously described such as in EP-A-0242081; U is aleaving group such as a halogen or CH₃ SO₂ --; V is hydrogen or a metal(such as sodium); and Y is a group which can be converted by standardprocedures described in the chemical literature into the group ZX. Thereactions shown in Schemes I and II are performed either in a suitablesolvent or without a solvent, and at a suitable temperature.

Thus compounds of formula (IA) (equivalent to compounds of the inventionwhen W is CH₃ O₂ C.C.═CH.OCH₃ and Z¹ is Z) can be prepared by treatmentof triazines of formula (IV) with phenols/thiophenols orphenolates/thiophenolates of formula (II) or by treatment of triazinesof formula (V) with substituted benzenes of formula (III) (Scheme I). Ineach case, the reaction is carried out in the presence of a base (suchas potassium carbonate) if V is hydrogen.

Compounds of formula (IB) (equivalent to the compounds of the inventionwhen W is CH₃ O₂ C.C═CH.OCH₃) can be prepared from triazines of formula(VI) (Scheme II). The term Y in formulae (VI), (VII) and (VIII)represents a group which can be converted by standard proceduresdescribed in the chemical literature into the group ZX--; for example, Ymay be a halogen (such as fluorine, chlorine or bromine) or --OH, --SH,--NHR⁴, --CO₂ H, ---COCl, --CHR¹ OH, --C(O)R¹, --CHR¹ --U (where U is aleaving group such as a halogen), --SO₂ OH, --SO₂ Cl, --CHR¹ P(O)(OR)₂or --CHR¹ P⁺ R₃ (counter-ion)⁻. Compounds of formula (VI) in which W isCH₃ O₂ C.C═CH.OCH₃ and Y has the values listed in the preceding sentenceare especially valuable intermediates for the preparation of thecompounds of the invention.

Triazines of formula (VI) can be prepared by treatment ofphenols/thiophenols or phenolates/thiophenolates of formula (II) withtriazines of formula (VII) or by treatment of substituted benzenes offormula (III) with triazines of formula (VIII) (Scheme II). In eachcase, the reaction is carried out in the presence of a base (such aspotassium carbonate) if V is hydrogen.

Modifications to the group W may be made at any appropriate stage in thepathways shown in Schemes I and II. For example, if W is the group --CH₂CO₂ CH₃ during the conversion of (VI) into (IB) (Scheme II), it may beconverted at the last stages of the synthesis into the group CH₃ O₂C.C═CH.OCH₃.

The substitutent A (one of K, L, M having the value CA wherein A is asdefined above) as well as any substituents on the carbocyclic orheterocyclic ring Z may also be modified at any appropriate reactionstep. If, for example, Y is a halogen such as chlorine, it may beremoved at an appropriate stage of the synthesis (such as the laststage) to give the corresponding triazine in which A is hydrogen.

Modifications to the linking group X (such as reducing an olefinic bondor oxidising a sulphur atom) may also be made at any appropriatereaction step.

Triazines of formulae (IV), (V), (VII) and (VIII) can be prepared bystandard methods described in the literature. Compounds of formulae (II)and (III) can also be made by standard methods or, when W is CH₃ O₂C.C═CH.OCH₃, can be made by methods described in EP-A-0242081 (T isoxygen) and EP-A-0178826 respectively.

In a further aspect the invention provides processes as herein-describedfor preparing the compounds of formula (I). It also provides anintermediate chemical of formula (VI).

The compounds are active fungicides and may be used to control one ormore of the following pathogens: Pyricularia oryzae on rice; Pucciniarecondita, Puccinia striiformis and other rusts on wheat, Pucciniahordei, Puccinia striiformis and other rusts on barley, and rusts onother hosts e.g. coffee, pears, apples, peanuts, vegetables andornamental plants; Erysiphe graminis (powdery mildew) on barley andwheat and other powdery mildews on various hosts such as Sphaerothecamacularis on hops, Sphaerotheca fuliginea on cucurbits (e.g. cucumber),Podosphaera leucotricha on apple and Uncinula necator on vines;Helminthosporium spp., Rhynchosporium spp., Septoria spp., Pyrenophoraspp., Pseudocercosporella herpotrichoides and Gaeumannomyces graminis oncereals; Cercospora arachidicola and Cercosporidium personata on peanutsand other Cercospora species on other hosts, for example, sugar beet,bananas, soya beans and rice; Botrytis cinerea (grey mould) on tomatoes,strawberries, vegetables, vines and other hosts; Alternaria spp. onvegetables (e.g. cucumber), oil-seed rape, apples, tomatoes and otherhosts; Venturia inaegualis (scab) on apples; Plasmopara viticola onvines; other downy mildews such as Bremia lactucae on lettuce,Peronospora spp. on soybeans, tobacco, onions and other hosts,Pseudoperonospora humuli on hops and Pseudoperonospora cubensis oncucurbits; Phytophthora infestans on potatoes and tomatoes and otherPhytophthora spp. on vegetables, strawberries, avocado, pepper,ornamentals, tobacco, cocoa and other hosts; Thanatephorus cucumeris onrice and other Rhizoctonia species on various hosts such as wheat andbarley, vegetables, cotton and turf.

Some of the compounds show a broad range of activities against fungi invitro. They may also have activity against various post-harvest diseasesof fruit (e.g. Penicillium digitatum and italicum and Trichoderma virideon oranges, Gloeosporium musarum on bananas and Botrytis cinerea ongrapes).

Further, some of the compounds may be active as seed dressings againstpathogens including Fusarium spp., Septoria spp., Tilletia spp., (bunt,a seed-borne disease of wheat), Ustilago spp. and Helminthosporium spp.on cereals, Rhizoctonia solani on cotton and Pyricularia oryzae on rice.

The compounds may move acropetally/locally in plant tissue. Moreover,the compounds may be volatile enough to be active in the vapour phaseagainst fungi on the plant.

The invention therefore provides a method of combating fungi whichcomprises applying to a plant, to a seed of a plant or to the locus ofthe plant or seed a fungicidally effective amount of a compound ashereinbefore defined, or a composition containing the same.

The compounds may be used directly for agricultural purposes but aremore conveniently formulated into compositions using a carrier ordiluent. The invention thus provides fungicidal compositions comprisinga compound as hereinbefore defined and an acceptable carrier or diluenttherefor. It is preferred that these compositions comprise 0.0001 to95%, more preferably 0.001 to 60%, even more preferably 0.01 to 1%, ofthe compound.

The compounds can be applied in a number of ways. For example, they canbe applied, formulated or unformulated, directly to the foliage of aplant, to seeds or to other medium in which plants are growing or are tobe planted, or they can be sprayed on, dusted on or applied as a creamor paste formulation, or they can be applied as a vapour or as slowrelease granules.

Application can be to any part of the plant including the foliage,stems, branches or roots, or to soil surrounding the roots, or to theseed before it is planted, or to the soil generally, to paddy water orto hydroponic culture systems. The invention compounds may also beinjected into plants or sprayed onto vegetation using electrodynamicspraying techniques or other low volume methods.

The term "plant" as used herein includes seedlings, bushes and trees.Furthermore, the fungicidal method of the invention includespreventative, protectant, prophylactic and eradicant treatments.

The compounds are preferably used for agricultural and horticulturalpurposes in the form of a composition. The type of composition used inany instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dustable powders or granulescomprising the active ingredient (invention compound) and a soliddiluent or carrier, for example, fillers such as kaolin, bentonite,kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia,fuller's earth, gypsum, diatomaceous earth and china clay. Such granulescan be preformed granules suitable for application to the soil withoutfurther treatment. These granules can be made either by impregnatingpellets of filler with the active ingredient or by pelleting a mixtureof the active ingredient and powdered filler. Compositions for dressingseed may include an agent (for example, a mineral oil) for assisting theadhesion of the composition to the seed; alternatively the activeingredient can be formulated for seed dressing purposes using an organicsolvent (for example, N-methylpyrrol-idone, propylene glycol orN,N-dimethylformamide). The compositions may also be in the form ofwettable powders or water dispersible granules comprising wetting ordispersing agents to facilitate the dispersion in liquids. The powdersand granules may also contain fillers and suspending agents.

Emulsifiable concentrates or emulsions may be prepared by dissolving theactive ingredient in an organic solvent optionally containing a wettingor emulsifying agent and then adding the mixture to water which may alsocontain a wetting or emulsifying agent. Suitable organic solvents arearomatic solvents such as alkylbenzenes and alkylnaphthalenes, ketonessuch as cyclohexanone and methylcyclohexanone, chlorinated hydrocarbonssuch as chlorobenzene and trichlorethane, and alcohols such as benzylalcohol, furfuryl alcohol, butanol and glycol ethers.

Suspension concentrates of largely insoluble solids may be prepared byball or bead milling with a dispersing agent with a suspending agentincluded to stop the solid settling.

Compositions to be used as sprays may be in the form of aerosols whereinthe formulation is held in a container under pressure of a propellant,e.g. fluorotrichloromethane or dichlorodifluoromethane.

The invention compounds can be mixed in the dry state with a pyrotechnicmixture to form a composition suitable for generating in enclosed spacesa smoke containing the compounds.

Alternatively, the compounds may be used in micro-encapsulated form.They may also be formulated in biodegradable polymeric formulations toobtain a slow, controlled release of the active substance.

By including suitable additives, for example additives for improving thedistribution, adhesive power and resistance to rain on treated surfaces,the different compositions can be better adapted for various utilities.

The invention compounds can be used as mixtures with fertilisers (e.g.nitrogen-, potassium- or phosphorus-containing fertilisers).Compositions comprising only granules of fertiliser incorporating, forexample coated with, the compound are preferred. Such granules suitablycontain up to 25% by weight of the compound. The invention thereforealso provides a fertiliser composition comprising a fertiliser and thecompound of general formula (I) or a salt or metal complex thereof.

Wettable powders, emulsifiable concentrates and suspension concentrateswill normally contain surfactants, e.g. a wetting agent, dispersingagent, emulsifying agent or suspending agent. These agents can becationic, anionic or non-ionic agents.

Suitable cationic agents are quaternary ammonium compounds, for example,cetyltrimethylammonium bromide. Suitable anionic agents are soaps, saltsof aliphatic monoesters of sulphuric acid (for example, sodium laurylsulphate), and salts of sulphonated aromatic compounds (for example,sodium dodecylbenzenesulphonate, sodium, calcium or ammoniumlignosulphonate, butylnaphthalene sulphonate, and a mixture of sodiumdiisopropyl- and triisopropylnaphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethyleneoxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkylphenols such as octyl- or nonylphenol and octylcresol. Other non-ionicagents are the partial esters derived from long chain fatty acids andhexitol anhydrides, the condensation products of the said partial esterswith ethylene oxide, and the lecithins. Suitable suspending agents arehydrophilic colloids (for example, polyvinylpyrrolidone and sodiumcarboxymethylcellulose), and swelling clays such as bentonite orattapulgite.

Compositions for use as aqueous dispersions or emulsions are generallysupplied in the form of a concentrate containing a high proportion ofthe active ingredient, the concentrate being diluted with water beforeuse. These concentrates should preferably be able to withstand storagefor prolonged periods and after such storage be capable of dilution withwater in order to form aqueous preparations which remain homogeneous fora sufficient time to enable them to be applied by conventional sprayequipment. The concentrates may conveniently contain up to 95%, suitably10-85%, for example 25-60%, by weight of the active ingredient. Afterdilution to form aqueous preparations, such preparations may containvarying amounts of the active ingredient depending upon the intendedpurpose, but an aqueous preparation containing 0.0005% or 0.01% to 10%by weight of active ingredient may be used.

The compositions of this invention may contain other compounds havingbiological activity, e.g. compounds having similar or complementaryfungicidal activity or which possess plant growth regulating, herbicidalor insecticidal activity.

A fungicidal compound which may be present in the composition of theinvention may be one which is capable of combating ear diseases ofcereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporiumspp., seed and soil-borne diseases and downy and powdery mildews ongrapes and powdery mildew and scab on apple, etc. By including anotherfungicide, the composition can have a broader spectrum of activity thanthe compound of general formula (I) alone. Further the other fungicidecan have a synergistic effect on the fungicidal activity of the compoundof general formula (I). Examples of fungicidal compounds which may beincluded in the composition of the invention are(±)-cis-1-(4-chlorophenyl)-2-(1H-1,2,4--triazol-1-yl) cycloheptanol,(2RS,3RS)-1-3-(2-chlorophenyl)-2-(4-fluoro-phenyl)oxiran-2-ylmethyl!-1H-1,2,4-triazole,(RS)-1-aminopropylphosphonic acid,(RS)-4-(4-chlorophenyl)-2-phenyl-2-(1H-1,2,4-triazol-1-ylmethyl)butyronitrile,(Z)-N-but-2-enyloxymethyl-2-chloro-2', 6'-diethylacetanilide,1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea,3-(2,4-dichlorophenyl)-2--(1H-1,2,4-triazol-1-yl)quinazolin-4(3H)-one,4-(2,2-difluoro-1,3-benzodi-oxol-4-yl)pyrrole-3-carbonitrile,4-bromo-2-cyano-N,N-dimethyl-6-trifluoro-methylbenzimidazole-1-sulphonamide,5-ethyl-5,8-dihydro-8-oxo(1,3)-dioxol-(4,5-g) quinoline-7-carboxylicacid, α- N-(3-chloro-2,6-xylyl)-2-methoxy-acetamido!-γ-butyrolactone,aldimorph, anilazine, benalaxyl, benomyl, biloxazol, binapacryl,bitertanol, blasticidin S, bromuconazole, bupirimate, buthiobate,captafol, captan, carbendazim, carboxin, chlorbenzthiazone, chloroneb,chlorothalonil, chlorozolinate, copper containing compounds such ascopper oxychloride, copper sulphate and Bordeaux mixture, cycloheximide,cymoxanil, cyproconazole, cyprofuram, di-2-pyridyl disulphide1,1'-dioxide, dichlofluanid, dichlone, diclobutrazol, diclomezine,dicloran, difenoconazole, dimethamorph, dimethirimol, diniconazole,dinocap, ditalimfos, dithianon, dodemorph, dodine, edifenphos,etaconazole, ethirimol, ethyl (Z)-N-benzyl-N-(methyl(methyl-thioethylideneamino-oxycarbonyl)amino!thio)-β-alaninate,etridiazole, fenapanil, fenarimol, fenfuram, fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, flutolanil, flutriafol,flusilazole, folpet, fosetyl-aluminium, fuberidazole, furalaxyl,furconazole-cis, guazatine, hexaconazole, hydroxyisoxazole, imazalil,imibenconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin,mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, methfuroxam,metsulfovax, myclobutanil, neoasozin, nickel dimethyldithiocarbamate,nitrothal-isopropyl, nuarimol, ofurace, organomercury compounds,oxadixyl, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazinoxide, phthalide, polyoxin D, polyram, poxin D, polyram, probenazole,prochloraz, procymidone, propamocarb, propiconazole, propineb,prothiocarb, pyrazophos, pyrifenox, pyroquilon, pyroxyfur, pyrrolnitrin,quinomethionate, quintozene, streptomycin, sulphur, tebuconazole,techlofthalam, tecnazene, tetraconazole, thiabendazole, thicyofen,thiophanate-methyl, thiram, tolclofos-methyl, triacetate salt of1,1'-iminodi(octamethylene)diguanidine, triadimefon, triadimenol,triazbutyl, tricyclazole, tridemorph, triforine, validamycin A,vinclozolin, zarilamid and zineb. The compounds of general formula (I)can be mixed with soil, peat or other rooting media for the protectionof plants against seed-borne, soil-borne or foliar fungal diseases.

Suitable insecticides which may be incorporated in the composition ofthe invention include buprofezin, carbaryl, carbofuran, carbosulfan,chlorpyrifos, cycloprothrin, demeton-s-methyl, diazinon, dimethoate,ethofenprox, fenitrothion, fenobucarb, fenthion, formothion, isoprocarb,isoxathion, monocrotophos, phenthoate, pirimicarb, propaphos and XMC.

Plant growth regulating compounds are compounds which control weeds orseedhead, formation, or selectively control the growth of less desirableplants (e.g. grasses).

Examples of suitable plant growth regulating compounds for use with theinvention compounds are 3,6-dichloropicolinic acid,1-(4-chlorophenyl)-4,6-di-methyl-2-oxo-1,2-dihydropyridine-3-carboxylicacid, methyl-3,6-dichloroanisate, abscisic acid, asulam,benzoylprop-ethyl, carbetamide, daminozide, difenzoquat, dikegulac,ethephon, fenpentezol, fluoridamid, glyphosate, glyphosine,hydroxybenzonitriles (e.g. bromoxynil), inabenfide, isopyrimol, longchain fatty alcohols and acids, maleic hydrazide, mefluidide,morphactins (e.g. chlorfluoroecol), paclobutrazol, phenoxyacetic acids(e.g. 2,4-D or MCPA), substituted benzoic acid (e.g. triiodobenzoicacid), substituted quaternary ammonium and phosphonium compounds (e.g.chloromequat, chlorphonium or mepiquatchloride), tecnazene, the auxins(e.g. indoleacetic acid, indolebutyric acid, naphthylacetic acid ornaphthoxyacetic acid), the cytokinins (e.g. benzimidazole,benzyladenine, benzylaminopurine, diphenylurea or kinetin), thegibberellins (e.g. GA₃, GA₄ or GA₇) and triapenthenol.

The following Examples illustrate the invention. Throughout theExamples, the term `ether` refers to diethyl ether, magnesium sulphatewas used to dry solutions, and solutions were concentrated under reducedpressure. Reactions involving water-sensitive intermediates wereperformed under an atmosphere of nitrogen and solvents were dried beforeuse, where appropriate. Unless otherwise stated, chromatography wasperformed on a column of silica gel as the stationary phase. Whereshown, infrared and NMR data are selective; no attempt is made to listevery absorption in all cases. ¹ H NMR spectra were recorded using CDCl₃solutions unless otherwise stated. (E)-Methyl2-(2-hydroxyphenyl)-3-methoxypropenoate, used as an intermediate in twoof the following Examples, was prepared as described in Example 3 ofEP-A-0242081. The following abbreviations are used throughout.

    ______________________________________                                        DMF = N,N-dimethylformamide                                                                        s = singlet                                              NMR = nuclear magnetic resonance                                                                   m = multiplet                                            IR = infrared        ppm = parts per million                                  m.p. = melting point                                                          ______________________________________                                    

EXAMPLE 1

This Example illustrates the preparation of (E)-methyl 2-2-(4-phenylthio-1,3,5-triazin-2-yloxy)-phenyl!-3-methoxypropenoate(Compound No. 1 of Table III).

To a stirred solution of 2,6-dichloro-1,3,5-triazine (0.3 g, 2 mmol;made according to R L N Harris, Synthesis, 1981, 907) and potassiumcarbonate (0.28g, 2 mmol) in dry acetonitrile (25 ml) at 0° C. under anatmosphere of nitrogen was added dropwise a solution of (E)-methyl2-(2-hydroxyphenyl)-3-methoxypropenoate (0.42 g, 2 mmol) in dryacetonitrile (7 ml). Anhydrous caesium fluoride (0.30 g, 2 mmol) and acatalytic amount of 18-crown-6 were added with stirring and thetemperature was allowed to rise to room temperature. After stirringovernight, the reaction mixture was filtered and evaporated to leave ayellow/orange paste. Chromatography (eluent diethyl ether) afforded(E)-methyl 2-2-(4-chloro-1,3,5-triazin-2-yloxy)phenyl!-3-methoxypropenoate (0.42 g)as a white solid, m.p. 137-140° C.; IR max. 1704, 1631 cm⁻¹ ; ¹ H NMR(CDCl₃) δ3.63(3H,s); 3.75(3H,s); 7.19-7.29(1H,m); 7.31-7.45(3H,m);7.47(1H,s); 8.74(1H,s) ppm.

Thiophenol (0.207 g, 1.88 mmol) and potassium carbonate (0.26 g, 1.88mmol) were stirred together in DMF (35 ml) at 60° C. After 15 minutes, asolution of (E)-methyl 2-2-(4-chloro-1,3,5-triazin-2-yloxy)phenyl!-3-methoxypropenoate (0.55g,1.71 mmol) in DMF (10 ml) was added and the mixture stirred at 60° C.for a further 2 hours. The reaction mixture was poured into water andthen extracted with ether (x3). The combined organic layers were washedwith dilute sodium hydroxide solution (x2) and water (x3), dried,filtered and evaporated to give a yellow gum (317 mg). Chromatography(eluent ether) afforded the title compound as a yellow solid (161 mg,25%); m.p. 119-121° C.; IR maxima 1712, 1632 cm⁻¹ ; ¹ H NMR as in TableVII.

EXAMPLE 2

This Example illustrates the preparation of (E)-methyl 2-2-(4-phenethyloxy-1,3,5-triazin-2-yloxy) -phenyl!-3-methoxypropenoate(Compound No. 96 of Table III).

Phenethyl alcohol (126 mg, 1.03 mmol) in dry DMF (5 ml) was added to asuspension of sodium hydride (45 mg, 1.03 mmol, 55% dispersion in oil)in dry DMF (5 ml). After stirring at room temperature under nitrogen for15 minutes, a solution of (E)-methyl 2-2-(4-chloro-1,3,5-triazin-2-yloxy)-phenyl!-3-methoxypropenoate (300 mg,0.933 mmol, prepared as described in Example 1) in DMF (10 ml) was addeddropwise and the resulting mixture was stirred overnight. The reactionmixture was diluted with water and then extracted with ether. Theorganic layers were washed with water, dried, filtered and evaporated.Chromatography of the residue (eluent ether) afforded the title compound(31 mg) as a yellow gum; ¹ H NMR as in Table VII; mass spectrum m/e 407(M⁺).

EXAMPLE 3

This Example illustrates the preparation (E)-methyl 2- 2-(6-chloro-3-2-methylphenylthio!-1,2,4-triazin-5-yloxy)phenyl!-3-methoxypropenoateand (E)-methyl 3-methoxy-2- 2-(3-2-methylphenylthio!-1,2,4-triazin-5-yloxy)-phenyl!propenoate (CompoundsNos. 360A and 360 respectively of Table II).

3,5,6-Trichloro-1,2,4-triazine (0.50 g) was dissolved in drytetrahydrofuran (8 ml) and dry potassium carbonate (0.37 g) and 4Åmolecular sieves (180 mg, activated overnight at 180° C.) were added.The stirred mixture was cooled to 0° C. and a solution of o-thiocresol(0.36 g) in dry tetrahydrofuran (4 ml) was added dropwise. After 45minutes at 0-5° C. and standing overnight at 10° C., the mixture wasdiluted with dichloromethane (20 ml) and filtered through Hyflo Supercelfilter aid covered with a layer of Merck silica 60. The filtrate wasconcentrated under reduced pressure to afford a singledichloro-(2-methylphenylthio)-1,2,4-triazine (unidentified regioisomer)as a yellow oil (0.86 g) which crystallised on standing.Recrystallisation from ether-n-hexane yielded a pale yellow powder (0.57g, 77%); m.p. 93-95° C.; IR max (nujol mull): 1460, 1250 cm⁻¹ ; ¹ H NMR:δ2.38 (3H,s), 7.24-7.37(1H,m), 7.37-7.54(3H,m) ppm.

To a stirred solution of thedichloro-(2-methylphenylthio)-1,2,4-triazine formed in the reactionabove (0.35 g) in dry acetonitrile (10 ml) was added dry potassiumcarbonate (0.18 g), followed by a solution of (E)-methyl2-(2-hydroxyphenyl)-3-methoxypropenoate (0.27 g) in dry acetonitrile (2ml), in one portion, at room temperature. A catalytic amount of18-crown-6 and dry caesium fluoride (0.20 g) were then added. Afterstirring at room temperature for 11.5 hours, the mixture was dilutedwith acetonitrile (25 ml) and filtered through Hyflo Supercel filteraid. The filtrate was concentrated under reduced pressure and theresidue was chromatographed twice using first ether-n-hexane (1:1) andthen n-hexane-dichloromethane-acetonitrile (16:4:1) as eluent to afford(E)-methyl 2- 2-(6-chloro-3-2-methylphenylthio!-1,2,4-triazin-5-yloxy)-phenyl!-3-methoxypropenoateas a pale yellow gum (0.16 g, 28%); IR max (nujol mull): 1710, 1630 cm⁻¹; ¹ H NMR δ2.27(3H,s), 3.64(3H,s), 3.75(3H,s), 6.90-6.97(1H,m),7.09-7.39(6H,m), 7.45-7.53(1H,m), 7.49(1H,s) ppm.

Potassium carbonate (0.115 g), 5% palladium on carbon (0.025 g) andwater (0.5 ml) were added to a solution of (E)-methyl 2- 2-(6-chloro-3-2-methylphenylthio!-1,2,4-triazin-5-yloxy)phenyl!-3-methoxypropenoate(0.106 g) in tetrahydrofuran (12 ml). Hydrogen gas was passed throughthe stirred mixture for 10.25 hours and then more dry potassiumcarbonate (0.100 g) and 10% palladium on carbon (0.030 g) were added.After hydrogen had been passed for a total of 21.25 hours, the mixturewas diluted with dichloromethane (15 ml) and water (10 ml) and filteredthrough Hyflo Supercel filter aid. The dichloromethane solution wasseparated from the filtrate and the aqueous layer was extracted withfurther dichloromethane (2×15 ml). The combined dichloromethane solutionand extracts were dried and concentrated under reduced pressure.Chromatography of the residue using ether-n-hexane (5:2) as eluentafforded (E)-methyl 3-methoxy-2- 2-(3-2-methylphenylthio!-1,2,4-triazin-5-yloxy!phenyl!propenoate as a paleyellow gum (23 mg) containing 21% of an unidentified impurity. IR max(dichloromethane solution): 1710, 1630cm⁻¹ ; ¹ H NMR δ2.31(3H,s),3.58(3H,s), 3.70(3H,s), 6.88-7.00(1H,m), 7.11-7.37(6H,m), 7.47(1H,s),7.49-7.57(1H,m), 8.59(1H,s) ppm.

The following are examples of compositions suitable for agricultural andhorticultural purposes which can be formulated from the compounds of theinvention. Such compositions form another aspect of the invention.Percentages are by weight.

EXAMPLE 4

An emulsifiable concentrate is made up by mixing and stirring theingredients until all are dissolved.

    ______________________________________                                        Compound No.1 of Table III                                                                          10%                                                     Benzyl alcohol        30%                                                     Calcium dodecylbenzenesulphonate                                                                    5%                                                      Nonylphenolethoxylate (13 moles                                                                     10%                                                     ethylene oxide)                                                               Alkyl benzenes        45%                                                     ______________________________________                                    

EXAMPLE 5

The active ingredient is dissolved in methylene dichloride and theresultant liquid sprayed on to the granules of attapulgite clay. Thesolvent is then allowed to evaporate to produce a granular composition.

    ______________________________________                                        Compound No.1 of Table III                                                                        5%                                                        Attapulgite granules                                                                              95%                                                       ______________________________________                                    

EXAMPLE 6

A composition suitable for use as a seed dressing is prepared bygrinding and mixing the three ingredients.

    ______________________________________                                        Compound No.1 of Table III                                                                        50%                                                       Mineral oil         2%                                                        China clay          48%                                                       ______________________________________                                    

EXAMPLE 7

A dustable powder is prepared by grinding and mixing the activeingredient with talc.

    ______________________________________                                        Compound No.1 of Table III                                                                        5%                                                        Talc                95%                                                       ______________________________________                                    

EXAMPLE 8

A suspension concentrate is prepared by ball milling the ingredients toform an aqueous suspension of the ground mixture with water.

    ______________________________________                                        Compound No.1 of Table III                                                                        40%                                                       Sodium lignosulphonate                                                                            10%                                                       Bentonite clay      1%                                                        Water               49%                                                       ______________________________________                                    

This formulation can be used as a spray by diluting into water orapplied directly to seed.

EXAMPLE 9

A wettable powder formulation is made by mixing together and grindingthe ingredients until all are thoroughly mixed.

    ______________________________________                                        Compound No.1 of Table III                                                                        25%                                                       Sodium lauryl sulphate                                                                            2%                                                        Sodium lignosulphonate                                                                            5%                                                        Silica              25%                                                       China clay          43%                                                       ______________________________________                                    

EXAMPLE 10

The compounds were tested against a variety of foliar fungal diseases ofplants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (No.1 or 2) in 4 cmdiameter minipots. The test compounds were formulated either by beadmilling with aqueous Dispersol T or as a solution in acetone oracetone/ethanol which was diluted to the required concentrationimmediately before use. For the foliage diseases, the formultions (100ppm active ingredient except where otherwise indicated) were sprayedonto the foliage and applied to the roots of the plants in the soil. Thesprays were applied to maximum retention and the root drenches to afinal concentration equivalent to approximately 40 ppm a.i. in dry soil.Tween 20, to give a final concentration of 0.05%, was added when thesprays were applied to cereals.

For most of the tests the compound was applied to the soil (roots) andto the foliage (by spraying) one or two days before the plant wasinoculated with the disease. An exception was the test on Erysiphegraminis in which the plants were incoulated 24 hours before treatment.Foliar pathogens were applied by spray as spore suspensions onto theleaves of test plants. After inoculation, the plants were put into anappropriate environment to allow infection to proceed and then incubateduntil the disease was ready for assessment. The period betweeninoculation and assessment varied from four to fourteen days accordingto the disease and environment.

disease control was recorded by the following grading:

4=no disease

3=trace-5% of disease on untreated plants

2=6-25% of disease on untreated plants

1=26-59% of disease on untreated plants

0=6-100% of disease on untreated plants

The results are shown in Table VIII.

                  TABLE VIII                                                      ______________________________________                                        Compound Table                                                                No       No     Pr     Egt  Sn  Po   Tc  Vi   Pv  Pil                         ______________________________________                                        1        III    4      4    4   3    --  --   4   --                          23       III    3.sup.a                                                                              0.sup.a                                                                            0.sup.a                                                                           0.sup.a                                                                            --  4.sup.a                                                                            4.sup.a                                                                           2.sup.a                     31       III    --     4    --  4    2   4    4   4                           96       III    4.sup.a                                                                              0.sup.a                                                                            3.sup.a                                                                           --   --  4.sup.a                                                                            4.sup.a                                                                           2.sup.a                     133      III    4.sup.a                                                                              0.sup.a                                                                            0.sup.a                                                                           --   --  4.sup.a                                                                            4.sup.a                                                                           4.sup.a                     322      III    4.sup.a                                                                              0.sup.a                                                                            3.sup.a                                                                           --   --  4.sup.a                                                                            4.sup.a                                                                           3.sup.a                     360      III    --     4    --  4    4   4    4   4                           361      III    0      1    0   1    0   0    4   0                           362      III    0.sup.a                                                                              0.sup.a                                                                            0.sup.a                                                                           0.sup.a                                                                            0.sup.a                                                                           1.sup.a                                                                            0.sup.a                                                                           0.sup.a                     ______________________________________                                         --No result                                                                   .sup.a 10 ppm foliar application only.                                        Key to Diseases                                                               Pr Puccinia recondita                                                         Egt Erysiphe graminis tritici                                                 Sn Septoria nodorum                                                           Po Pyricularia oryzae                                                         Tc Thanatephorus cumcumeris                                                   Vi Venturia inaequalis                                                        Pv Plasmopara viticola                                                        Pil Phytophthora infestans lycopersici                                   

    ______________________________________                                        CHEMICAL FORMULAE                                                             (in description)                                                              ______________________________________                                         ##STR2##                                                                     1                             (I)                                             2 #STR3##                                                                     3 #STR4##                     (I.1)                                           4 #STR5##                     (I.2)                                           ______________________________________                                    

                  TABLE I                                                         ______________________________________                                         ##STR6##                                                                     5                             (I.3)                                           ______________________________________                                    

                  TABLE II                                                        ______________________________________                                         ##STR7##                                                                     6                             (I.4)                                           ______________________________________                                    

                  TABLE III                                                       ______________________________________                                         ##STR8##                                                                     7                             (I.5)                                           ______________________________________                                    

                  TABLE IV                                                        ______________________________________                                         ##STR9##                                                                     8                             (I.6)                                           ______________________________________                                    

                  TABLE V                                                         ______________________________________                                         ##STR10##                                                                    9                             (I.7)                                           ______________________________________                                    

                  TABLE VI                                                        ______________________________________                                         ##STR11##                                                                    0                             (I.8)                                           * X for Compound No 117 is                                                    1 #STR12##                                                                    * X for Compound No 118 is                                                    2 #STR13##                                                                    * Z for Compound No 315 is                                                    3 #STR14##                                                                    ______________________________________                                         ##STR15##

We claim:
 1. A compound having the formula (I): in which any two of K, Land M are nitrogen and the other is CA wherein A is H, halogen, C₁₋₄alkyl, C₁₋₄ alkoxy, cyano, nitro or trifluoromethyl;X is selected fromthe group consisting of S(O)_(n), NR⁴ N(CHO), CR¹ R² CHR⁶, CO, CR¹(OR²), C═CR¹ R², CHR¹ CHR², CR¹ ═CR², CHR¹ CR² ═CH, C.tbd.C, OCHR¹, CHR¹O, CH(CF₃)O, CH(CN)O, OCHRO¹ O, S(O)_(n) CHR¹, S(O)_(n) CHR¹ O, CHR¹S(O)_(n), CHR¹ OSO₂ NR⁴ CHR¹, CHR¹ NR⁴, CO₂, O₂ C, SO₂ O, OSO₂, CO.CO,COCHR¹, COCHR¹ O, CHR¹ CO, CHOH.CHR¹, CHR¹.CHOH, ##STR16## CONR⁴,OCONR⁴, NR⁴ CO, CSNR⁴, OCS.NR⁴, SCO.NR⁴, NR⁴ CO₂, NR⁴ CS, NR⁴ CSO, NR⁴COS, NR⁴ CONR⁴, S(O)_(n) NR⁴, NR⁴ S(O)_(n), CS₂, S₂ C, CO.S., SCO, N═N,N═CR¹, CR¹ ═N, CHR¹ CHR² CH(OH), CHR¹ OCO, CHR¹ SCO, CHR¹ NR⁴ CO, CHR¹NR⁴ CONR⁴, CHR¹ CHR² CO, O.N═CR¹, CHR¹ O.N═CR², CO.OCR¹ R², CHR¹ CHR²CHR³, OCHR¹ CHR², (CH₂)_(m) O, CHR¹ OCHR², CHR¹ CHR² O, OCHR¹ CHR² O,S(O)_(n) CHR¹ CHR², SCHR¹ CHR² O, CHR¹ S(O)_(n) CHR², CHR¹ CHR²S(O)_(n), CR¹ ═NNR⁴, CR¹ ═NO, NR⁴ N═CR¹, CHR¹ CONR², CHR¹ OCO.NR²,CH═CHCH₂ O C.tbd.CCH₂ O, COCHR¹ CHR² O, and (R⁵)₂ P⁺ CHR² Q⁻ ; where R¹,R² and R³, which may be the same or different, are H, C₁₋₄ alkyl orphenyl; R⁴ is H, C₁₋₄ alkyl or COR¹ ; R⁵ is optionally substitutedphenyl; R⁶ is substituted phenyl; Q⁻ is a halide anion; n is 0, 1 or 2;and m is 3, 4 or 5; T is oxygen or sulphur; and Z is a carbocyclic ringoptionally substituted with one or more of the following: halo, hydroxy,oxo, mercapto, C₁₋₄ alkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₁₋₄ alkoxy, C₂₋₄alkenyloxy, C₂₋₄ alkynyloxy, halo(C₁₋₄)alkyl, halo(C₁₋₄)alkoxy, C₁₋₄alkylthio, hydroxy(C₁₋₄)alkyl, C₁₋₄ alkoxy(C₁₋₄)alkyl, C₃₋₆ cycloalkyl,C₃₋₆ cycloalkyl(C₁₋₄)alkyl, optionally substituted aryl, optionallysubstituted aryloxy, optionally substituted aryl(C₁₋₄)alkyl, in whichthe alkyl moiety is optionally substituted with hydroxy, optionallysubstituted aryl(C₂₋₄)alkenyl, optionally substituted aryl(C₁₋₄)alkoxy,optionally substituted aryloxy(C₁₋₄)alkyl, acyloxy, cyano, thiocyanato,nitro, --NR'R", --NHCOR', --NHCONR'R", --CON'R", --COOR', --OSO₂ R',--COR', --CR'═NR" or --N═CR'R" in which R' and R" are independentlyhydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ alkylthio, C₃₋₆ cycloalkyl, C₃₋₆cycloalkyl(C₁₋₄)alkyl, phenyl or benzyl, the phenyl and benzyl groupsbeing optionally substituted with halogen, C₁₋₄ alkyl or C₁₋₄ alkoxy, orany two substituents of the carbocyclic ring Z when adjacent to oneanother, may together with the carbon atoms to which they are attachedjoin to form a 5- or 6-membered ring; substituents which may be presentin the aryl rings of any of the foregoing substituents and in the phenylrings of R⁵ and R⁶ being one or more of the following: halo, hydroxy,mercapto, C₁₋₄ alkyl, C₂₋₄ alkenyl, C₂₋₄ alkenyloxy, C₂₋₄ alkynyloxy,halo(C₁₋₄)alkyl, halo(C₁₋₄)alkoxy, C₁₋₄ alkylthio, hydroxy(C₁₋₄)-alkyl,C₁₋₄ alkoxy(C₁₋₄)alkyl, C₃₋₆ cycloalkyl, C₃₋₆ cycloalkyl-(C₁₋₄)alkyl,alkanoyloxy, benzoyloxy, cyano, thiocyanato, nitro, --NR'R", --NHCOR',--NHCONR'R", --CON'R", --COOR', --OSO₂ R', --COR', --CR'═NR" or--N═CR'R" in which R' and R" have the meanings given above.
 2. Acompound according to claim 1 in which K and M are both nitrogen; L isCH; and Z is optionally substituted phenyl.
 3. A compound according toclaim 1 in which Z is selected from the group consisting of phenyl,naphthyl, cyclopentyl, cyclohexyl or cyclohexenyl, any of which isoptionally substituted.
 4. A compound having the formula (I.1) ##STR17##in which Z is phenyl optionally substituted with halo, C₁₋₄ alkyl ortrifluoromethyl; and X is S, CH₂ O, CH₂ S, CH₂ CH₂ O, CH₂ CH₂ CH₂ O or(E)--CH═NO.
 5. A compound having the formula (I.2): ##STR18## in which Zis phenyl optionally substituted with C₁₋₄ alkyl; X is S; and A is H orCl.
 6. A fungicidal composition comprising a fungicidally effectiveamount of a compound according to claim 1 and a fungicidally acceptablecarrier or diluent therefor.
 7. A method of combating fungi whichcomprises applying to plants, to the seeds of plants or to the locus ofthe plants or seeds, a compound according to claim 1 or a compositionaccording to claim
 4. 8. A compound in accordance with claim 1 wherein Xis selected from the group consisting of NR⁴, N(CHO), CR¹ R², CHR⁶, CO,CR¹ (OR²), C═CR¹ R², CHR¹ CHR², CR¹ ═CR², CHR¹ CR² ═CH, C═C, OCHR⁷, CHR¹O, CH(CF₃)O, CH(CN)O, OCHR¹ O, S(O)_(n) CHR¹, S(O)_(n) CHR¹ O, CHR¹S(O)_(n), CHR¹ OSO₂ NR⁴ CHR¹, CHR¹ NR⁴, CO₂, O₂ C, SO₂ O, OSO₂, CO.CO,COCHR¹, COCHR¹ O, CHR¹ CO, CHOH.CHR¹, CHR¹.CHOH, ##STR19## CONR⁴,OCONR⁴, NR⁴ CO, CSNR⁴, OCS.NR⁴ SCO.NR⁴, NR⁴ CO₂, NR⁴ CS, NR⁴ CSO, NR⁴COS, NR⁴ CONR⁴, S(O)_(n) NR⁴, NR⁴ S(O)_(n), CS₂, S₂ C, CO.S., SCO, N═N,N═CR¹, CR¹ ═N, CHR¹ CHR² CH(OH), CHR¹ OCO, CHR¹ SCO, CHR¹ NR⁴ CO, CHR¹NR⁴ CONR⁴, CHR¹ CHR² CO, O.N═CR¹, CHR¹ O.N═CR², CO.OCR¹ R², CHR¹ CHR²CHR³, OCHR¹ CHR², (CH₂)_(m) O, CHR¹ OCHR², CHR¹ CHR² O, OCHR¹ CHR² O,S(O)_(n) CHR¹ CHR², SCHR¹ CHR² O, CHR¹ S(O)_(n) CHR², CHR¹ CHR²S(O)_(n), CR¹ ═NNR⁴, CR.sup. ═NO, NR⁴ N═CR¹, CHR¹ CONR², CHR¹ OCO.NR²,CH═CHCH.₂ O, C═CCH₂ O, COCHR¹ CHR² O, and (R⁵)₂ P⁺ CHR² Q⁻ ; where R¹,R² and R³, which may be the same or different, are H, C₁₋₄ alkyl orphenyl; R⁴ is H, C₁₋₄ alkyl or COR¹ ; R⁵ is optionally substitutedphenyl; R⁶ is substituted phenyl; R⁷ is C₁ -C₄ alkyl or phenyl; Q⁻ is ahalide anion; n is 0, 1 or 2; and m is 3, 4 or 5.